Corrosion Science 153 (2019) 200–212

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Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Effect of Zro2 particles on oxidation and electrical behavior of Co coatings T

electroplated on ferritic stainless steel interconnect
⁎
Fatemeh Saeidpoura,b, Morteza Zandrahimia, , Hadi Ebrahimifarc
a
Department of Metallurgy and Materials Science, Faculty of Engineering, Shahid Bahonar University of Kerman, Jomhoori Eslami Blvd., Kerman, Iran
b
Department of Materials Engineering, Esfarayen University of Technology, Esfarayen, North Khorasan Province, Iran
c
Department of Materials Engineering, Faculty of Mechanical and Materials Engineering, Graduate University of Advanced Technology, Kerman, Iran

A R T I C LE I N FO A B S T R A C T

Keywords: The application of protective coatings has been proposed to overcome the difficulties in utilizing ferritic stainless
Crofer 22 APU steels as interconnects. Co and Co/ZrO2 coatings are electroplated onto Crofer22APU, and their oxidation and
Co electrical behavior are evaluated in this paper. Cyclic oxidation is done in laboratory air at 800 °C for 500 h,
ZrO2 oxidation rates and oxide layer microstructures are examined. SEM–EDS and XRD investigations exhibit the
Oxidation
thicknesses of Cr2O3 scale, and oxidation rates are decreased for Co/ZrO2 coated steels relative to Co-coated and
Electrical behavior
uncoated steels. The ASR value of the Co/ZrO2 coated steel is 14.5 mΩ cm2 after cyclic oxidation at 800 °C.

1. Introduction Some alternative methods consisting of applying coatings and

modifying alloy composition have been employed to resolve the diffi-
Many attempts have been dedicated to the progression of inter- culties. The application of a conductive coating is relatively easy and
mediate-temperature solid oxide fuel cells (SOFCs) in order to enhance less expensive than alloy design [11]. Cubic spinels are a kind of the
the lengthy cycle stability, decrease the expenses and supply further cell main favorable coating materials, the conventional formula of which is
material selections [1]. Recent developments have reduced the opera- AB2O4. Depending on the selection of A and B ions and their propor-
tion temperature of SOFCs to about 600–800 °C, which makes metallic tions, spinels can have high electrical conductivity and show compa-
alloys attainable for interconnect, for example, Fe-, Ni-, Cr- and Co- tible thermal expansion with the FSS substrate and other cell compo-
based alloys [2]. Among these alloys, ferritic stainless steels (FSSs) are nents. Moreover, spinel coatings have a good ability for preventing the
promising candidates for utilization as SOFC interconnect because of evaporation of Cr species [12]. For example, MnCo2O4-based coatings
their fairly high-temperature oxidation resistance, good electronic and are able to obstruct important development of Cr2O3 layers and also Cr
heat conductivities, acceptable mechanical behavior, relatively low migration [13]. However, applying a more efficient coating by a more
expense and compatible thermal expansion with their neighbor cell effective coating method is necessary to increase the high-temperature
components [3–5]. Thus far, a variety of FFS grades have been con- oxidation resistance compared to cobalt-based spinels, which could
sidered for SOFC interconnect utilization, but Crofer 22 APU is cur- improve the lifetime of SOFCs.
rently one of the most popular FSSs, which was previously studied in Reactive elements oxides have been proven to considerably improve
[6]. The reason is that FFSs are mainly evaluated to have sufficiently layer adhesion and increase oxidation resistance. In spite of increasing
good oxidation resistance at high temperatures and they also contain Cr electrical conductivity, they are not appropriate as obstacles for Cr
which reacts with oxygen anions to create a compact and uninterrupted vaporization because they are usually thin and porous, and cannot be
surface oxide layer to prevent the corrosion of the substrate alloy [7]. In efficient in suppressing Cr migration toward the surface of interconnect
spite of these benefits, the development of surface oxide layers over and inhibiting Cr poisoning [14]. Reactive elements are effective since
time increases the electrical resistance of the FSS interconnect [8–10]. they can be deposited as surface oxide layers [15,16], added as alloying
Furthermore, the evaporation of Cr in the form of CrO2(OH)2 from the elements and/or spread as oxides [17,18]. An effective coating method
interconnect steel into the electrolyte-cathode gas interface, which can is the incorporation of Co-based spinels into the reactive element oxide
deposit on the SOFC cathode and electrolyte, leads to the performance inside single coating for decreasing Cr migration toward the surface of
degradation in SOFC stacks [7]. the metallic interconnect and increasing the oxidation resistance.

⁎
Corresponding author.
E-mail addresses: [email protected] (F. Saeidpour), [email protected] (M. Zandrahimi), [email protected] (H. Ebrahimifar).

https://doi.org/10.1016/j.corsci.2019.03.034
Received 22 August 2018; Received in revised form 10 March 2019; Accepted 13 March 2019
Available online 26 March 2019
0010-938X/ © 2019 Elsevier Ltd. All rights reserved.
F. Saeidpour, et al. Corrosion Science 153 (2019) 200–212

Table 1
Chemical composition of Crofer 22APU stainless steel.
Element C Cr Mn Si Ni Al Ti La Fe

Concentration (wt %) 0.01 22.7 0.38 0.02 0.02 0.02 0.07 0.06 Bal

Previous studies have confirmed the effectiveness of this method

[19,20].
In the present work, Co and Co-ZrO2 coatings are fabricated on
Crofer 22 APU by using electroplating technique. The oxidation re-
sistance and area specific resistance (ASR) of the Co and Co-ZrO2 coated
steels were likewise evaluated by an effort to exhibit the effect of ZrO2
on the properties of the coating.

2. Materials and experimental methods

Fig. 1. Thermal cycle diagram with data on thermal transients for oxidation test
for three cycles.
Crofer 22APU stainless steel sheet, manufactured by ThyssenKrupp
VDM GmbH (the chemical compositions are listed in Table 1), was used
as a metallic substrate for electrodeposition. Crofer 22 APU sheet was samples was measured before and after the high temperature exposure
wire-cut into 10 × 10 mm2 samples and total thickness was 2 mm. The and the weight gains were calculated as well. Three samples of each
surfaces of all the samples were ground with 240–2500 grit SiC paper, steels were oxidized in an electrical furnace for 500 h in laboratory air
washed in distilled water and then degreased with acetone in an ul- at 800 °C. The average mass gains were calculated for 3 samples. In-
trasonic cleaner for 20 min. Before the electroplating process, the spe- dividual mass gains were reproducible within ± 5%.
cimens were weighed and, then, pickled in a 5% HNO3 and 25% HCl Surface chemistry and morphology were analyzed by utilizing the
solution for 2 min to activate the surface. Afterward, they were elec- scanning electron microscopy (SEM), (CamscanMV2300) by energy
troplated in a plating bath with 90 g/l of CoCl2.6H2O and 90 ml/l of dispersive X-ray (EDX) analysis. The phase composition of the oxidation
37% HCl to form a very thin strike layer of Co before the coating step. products created on the uncoated and coated samples was characterized
The strike detaches the natural oxide scale from the surface of the by the means of X-ray diffraction (XRD) with a Philips X’Pert High Score
sample and, then, creates a Co layer with a very thin thickness and diffractometer by using Cu Ka (k = 1.5405 A°). The cross-sections of the
improves the adhering of the following coating layers [19]. steels were analyzed by utilizing SEM with EDX elements line scan
The samples were coated by using electroplating technique with analysis to observe the distribution profile of the elements on the cross-
pure Co and Co/ZrO2 coatings at 45 °C for 15 min. Electroplating was sections.
performed in a modified Watts bath with composition and operating The temperature-dependence of the ASR of the Co-coated, Co/ZrO2-
conditions shown in Table 2. For electroplating processes, Crofer coated, and uncoated oxidized samples were evaluated within
22APU (cathode) was located uprightly inside the bath, parallel to 650–800 °C after 500 h of cyclic oxidation in laboratory air at 800 °C.
unadulterated Co (anode). The ZrO2 particles were scattered in the bath ASR evaluation tests were conducted by using the setup shown in Fig. 2.
with a magnetic stirrer during electroplating. All the tests were per- Before testing, Ag paste was applied to the sample surface; then, an Ag
formed in 100 ml of electrolytes made ready by deionized water. The mesh was placed on it and Ag wires as the electrical conductor were
particle size of ZrO2 in deposition bath was measured by a light phase mounted to the samples. During the test, by applying a fixed current
scatter analyzer (Zetasizer -Vasco3). To modify the electrolyte pH, with the density of 500 mA cm−2 to the samples, the voltage was in-
NH4OH or 20 vol% H2SO4 was utilized. The space between Crofer scribed by using an Autolab Pgstat 302. The ASR was obtained by
22APU and unadulterated Co was 3 cm and the anode to cathode sur- multiplying R in the area of the Ag layer (cm2).
face proportion was 2, so that the polarization effect was decreased
[21]. 3. Results and discussion
After electrodeposition, the cyclic oxidation tests of uncoated, Co-
coated and Co/ZrO2-coated steels were conducted in a box furnace with 3.1. Microstructures and compositions of as-electroplated coating
a dry static laboratory air atmosphere. Cyclic thermal oxidation tests
were also performed for up to 20 cycles. Every cycle included a 25 h Fig. 3a and b show the surface morphology of the steel with
duration at 800˚C followed by 20 min of cooling at 25 °C. The heating
rate was about 5 °C/min and cooling rate was almost 25 °C/min for
oxidation tests. Fig. 1. Shows thermal cycle diagram with data on
thermal transients for oxidation test for three cycle. The weight of the

Table 2
Composition and operating conditions for electroplating of Co and Co/ZrO2 on
Crofer 22APU.
Cobalt sulphate heptahydrate, CoSO4.7H2O 100 g/L
Cobalt chloride hexahydrate, CoCl2.6H2O 10 g/L
Boric acid, H3BO3 20 g/L
Zirconium oxide, ZrO2 0–20 g/L
pH 3
Temperature 45 °C
Agitation Magnetic bar from the bottom
Anode Pure cobalt
Operating time 15 min
Fig. 2. Schematic figure of the experimental setup utilized for measuring the
Current density 25 mA/cm2
ASR.

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Fig. 3. Secondary electron image (a,b) and EDX analysis (c) of the surface of the as-deposited Co/ZrO2 coatings on Crofer 22 APU.

Fig. 4. Particles size dispersion of ZrO2 reinforcement powder by intensity at pH of 3.

composite coatings obtained by means of electroplating technique. coating was 1–5 μm, showing that some of ZrO2 particles were ag-
Fig. 3a shows that ZrO2 particles were successfully co-deposited into the glomerated during the electroplating process. Mean particle size of
Co matrix and had a uniform distribution. Surface morphology of ZrO2 powders in bath deposition was measured about 1.5 μm (Fig. 4)
coating was continuous, uniform and very dense with none large-scale whereas the size of ZrO2 particles in the coating was 1–5 μm (Fig. 3a),
pores or cracks. According to Fig. 3b, the Co matrix with needle-like indicating that ZrO2 particles have agglomerated during electro-
grains can be found on the substrates, and ZrO2 particles were clearly deposition.
observed in the Co matrix coating. The size of the ZrO2 particles in the These particles had a spherical shape and seemed poriferous. EDX

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Fig. 5. SEM cross-section image and EDS line scan of the: (a, b) Co-coated and (c, d) Co/ZrO2-coated samples.

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Fig. 6. Oxidation kinetics of the steels in laboratory air for 500 h at 800 °C expressed as: (a) weight gain for uncoated, (b) squared weight gain for uncoated, (c)
weight gain for Co-coated, (d) squared weight gain for Co-coated, (e) weight gain for Co/ZrO2 -coated and (f) squared weight gain for Co/ZrO2 coated samples as a
function of time in cyclic oxidation (time period in which the parabolic rate law is followed, is shown inside the parentheses).

analysis (Fig. 3c) that was carried out on the overall surface of the temperatures due to the volatility of chromium oxides. Therefore, these
coating (Fig. 3a) exhibited that Co, Zr and O amounts (weight percent) results are usually utilized for comparing the oxidation resistance of the
in the coating were 50. 5%, 33.5%, and 16. 0% respectively, verifying samples.
the electroplated coating included Co, Zr and O. Fig. 6 shows the kinetics of the oxidation of the uncoated, Co coated
Fig. 5 shows SEM cross-section images with EDS line scan of the Co- and Co/ZrO2 coated steels, indicated weight gains (Fig. 6a,c,e) and
coated (Fig. 5a, b) and Co/ZrO2-coated (Fig. 5c, d) samples. These squared weight gains (Fig. 6b,d,f) as a function of time oxidation in air
coatings were electroplated with the unvarying thicknesses of ap- at 800 °C. In Fig. 6b, d and f, the square area-specific mass change
proximately 5 μm and adhered to the Crofer 22APU substrate well with versus the oxidation time is plotted. Based on Wagner's oxidation
no cracks or separation in the direction of the interface, although a few theory [22], if the curve of the square area-specific mass change versus
small cracks can be seen in the interface of Co-coating and substrate. the oxidation time is a straight line, the growth is diffusion-controlled
The ZrO2 particles in the cross-section of the Co/ZrO2 coating are also and follows parabolic rate kinetics. The oxidation kinetics of the ex-
visible in Fig. 5c. They can be perceived by EDS analysis as well amined specimens almost followed the parabolic kinetics law. The
(Fig. 5d). Pilling–Bedworth Eq. (1) was utilized to evaluate the parabolic rate
constant (kp) [23].

3.2. Oxidation kinetics 2

⎛ δm ⎞ = kp × t + C
⎝ A ⎠ (1)
For evaluating the oxide layer growth rates of the samples, the
weight change per unit area was measured as a function of oxidation where δw is the weight change, A is the steel surface area, kp is the
time. However, the use of weight change for determining the oxidation parabolic rate constant, t is the oxidation time and C is an integration
resistance of chromium-containing alloys is not correct at high constant, explaining the start of parabolic kinetics. This behavior of the

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Fig. 7. Secondary electron images of: (a,b) uncoated Crofer 22APU, (c,d) Co-coated and (e,f) Co/ZrO2-coated samples after 500 h of cyclic oxidation at 800 °C.

Table 3 uncoated and coated steels is caused by the fact that Cr2O3 layer growth
EDS analysis data for the spots shown in Fig. 7b (compositions in weight. %). follows the parabolic rate law [24]. kp values of uncoated steel from 0
Spot Element
to 500 h was 5.3 × 10−13 mg2 cm−4s−1 due to the growth of Cr2O3
scale which slowly increase by increasing the oxidation time (Fig. 6a,
Cr O Mn Fe b). The Co-coated and Co/ZrO2-coated steels had a first quick mass gain
(kp = 3.3 × 10-12 for Co coated (Fig. 6d) and kp = 2.0 × 10−12 for Co/
1 37.61 40.4 21.99 0.00
ZrO2 coated (Fig. 6f) steels) and, afterwards, the mass gain raised very
2 39.46 34.37 18.98 7.19
slightly (kp = 3.4 × 10−13 for Co coated (Fig. 6d) and

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and stopping Cr poisoning [14]. In conformity with the information on

the oxidation kinetics of steels acquired after cyclic oxidation experi-
ments, weight gain rates of the uncoated and Co coated steels was
higher than the oxidation rate of the coated Crofer 22 APU with Co/
ZrO2 composite coating after 500 h of oxidation time in air at 800 °C
(Fig. 6) and the useful effect of ZrO2 particles in Co coating as re-
inforcement for the thermal protecting of Crofer 22APU was confirmed.

3.3. Microstructure and chemical composition of oxidized samples

Failure of the oxide layer is generally increased during cyclic oxi-

dation tests relative to isothermal oxidation tests. Thus, the oxidation
behavior in the process of thermal cycling further indicates of what is
occurring to the materials at the time of being exposed to operating
conditions. Entirely the ability of coatings to remain well adhered
during thermal cycling is an important property for SOFC applications.
Hence, the cyclic oxidation test was selected for evaluating the effect of
oxidation on the microstructure and chemical composition of the
samples [22,25–27].
After 500 h of cyclic oxidation, an oxide layer was observed on the
uncoated sample surface, as shown in Fig. 7a. The oxide layer was
principally made up of a black oxide layer and over this continuous
outer layer, some loose pyramidal grains or obvious small islands could
be observed in the direction of the grain boundaries of the steel (Fig. 7a,
b). It shows more oxidation above the grain boundaries of the substrate.
As seen, the scale is covered by the octahedral crystals particles
(Fig. 7b). The arrangement of these faceted particles (Fig. 7a, b) pro-
poses strongly that they have formed preferentially at locations where
the alloy grain boundaries intersect with the surface. It should be
considered that the grain boundary diffusion of transition metals
through Cr2O3 is 3–5 orders of magnitude faster than the bulk diffusion
[12]. The diameter of these well-developed grains is from around 10 μm
to about 50 μm. Both EDS data obtained from surface and cross section
of oxidizes sample imply that these 0.5–2.5 μm octahedrons are the
MnCr2O4 and FeCr2O4 spinle phases (see Table 3b and Fig. 7b). As these
particles consist mainly of Mn, Cr and O together with some Fe, it may
inferred that these are cubic chromium manganese spinel with a small
amount of FeCr2O4 spinel phase. The formation of MnCr2O4 spinel is
caused by fast diffusion of manganese along the ferrite and Cr2O3 grain
boundaries; on the surface, Mn reacts with the initially formed Cr2O3
and with the inwardly diffused O anions to form the spinel phase [12].
XRD analysis (Fig. 8a) also confirmed these results.
Fig. 7c and d demonstrate the surface morphology of Co-coated steel
after 500 h of cyclic oxidation in laboratory air at 800 °C. Oxide surface
includes pyramidal particles and the XRD analysis verifies (Fig. 8b) that
they are Co3O4 and MnCo2O4 spinels with a little amount of MnCr2O4
and FeCr2O4, which were approximately dense after 500 h of oxidation.
Fig. 8. XRD pattern of: (a) uncoated sample, (b) Co-coated sample and (c) Co/
ZrO2-coated sample after 500 h of cyclic oxidation in air at 800 °C.
The FeCr2O4, Co3O4 and MnCo2O4 phases have the same crystal
structure (cubic) and similar lattice parameters: a = b = c = 8.3640 A
for FeCr2O4, a = b = c = 8.0850 A for Co3O4, and a = b =
kp = 1.1 × 10−13 for Co/ZrO2 coated (Fig. 6f) steels) after 100 h of c = 8.2000 A for MnCo2O4. Therefore, FeCr2O4, Co3O4 and MnCo2O4
oxidation. The reason could be that the first oxidation of Co was an- phases can overlap with each other.
ticipated to occur quickly and was completely oxidized after 100 h in The oxide layer composed on the surface of the Co/ZrO2-coated
air at 800 °C [19]. This showed that the oxidation production of Co sample was denser and had smaller crystal size than the one composed
coating layer reduced the oxidation rate that was an effective factor for on the Co-coated sample surface (Fig. 7e, f). Furthermore, no important
overlong working cycle because it could result in the development of a marks of spallation or crack were seen on the surface of the Co/ZrO2-
Cr2O3 scale with high ASR. Weight gains of the Co/ZrO2-coated sample coated samples after cyclic oxidation. XRD analysis (Fig. 8c) verified
had a very lower rate than the uncoated and Co-coated steels after that the compositions of the surface oxide layers created on the Co-
100 h. Cr evaporation was not examined here; however, it would just coated and Co/ZrO2-coated samples were similar. Some of the ZrO2
enhance the distinction between uncoated and coated steels due to the particles, visible on the surface as-deposited Co/ZrO2 steel (Fig. 3a, b),
point that the Cr migration from the uncoated steel was seemingly were inserted in the Co oxide (Fig. 7e, f), which grew due to the dif-
higher. Although the reactive elements oxides remarkably improve fusion of metal ions [19], but some of them were still visible on the
coating adhesion and decrease oxidation rate and in addition, increase surface of steel after oxidation tests.
the electrical conductivity of the surface layer, they are not useful as the Fig. 9a and b show the polished cross-sectional images and EDX
limits of Cr evaporation because they have naturally low thickness, are elements line scan of the uncoated Crofer 22APU after 500 h cyclic
porous and cannot be efficient in preventing Cr migration to the surface oxidation in laboratory air at 800 °C. As can be seen, the surface scale

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Fig. 9. SEM cross-section image and EDS line scan of: (a, b) uncoated, (c, d) Co-coated and (e, f) Co/ZrO2-coated samples after 500 h of cyclic oxidation at 800 °C.

composed on the uncoated Crofer 22APU consisted of the internal layer Cr2O3 grain boundaries. Mn reacted with Cr2O3 that was at first created
of Cr-rich oxide and Mn-Cr-rich oxide on the external surface, corre- on the surface and the O anions diffused towards the inside in order to
sponding to other studies [23,24,28]; the thickness of this oxide scale is create the spinel phase [22].
about 2 μm, as exhibited in Fig. 9a. XRD analysis (Fig. 8a) confirmed Fig. 9c and d show the polished cross-sectional images and elements
that thin inner oxide layer consisted of Cr2O3 and outer oxide layer was line scan of the Co-coated Crofer 22APU after 500 h cyclic oxidation in
composed of MnCr2O4 and FeCr2O4. It could be concluded that surface laboratory air at 800 °C. Oxide layer composed on the Co-coated Crofer
of the uncoated one was covered with Cr2O3 and, then over this oxide 22APU included the internal layer of Cr-rich oxide with Co oxide and
layer, was slowly encased by MnCr2O4 spinels and a little amount of Co-Mn spinle layer on the external surface, corresponding to other
FeCr2O4 spinles as oxidation time increased. Even though Crofer 22 studies [22,29]. Fig. 9c shows that the external Co spinel layer was
APU steel included lower than 1%Mn, the existence of Mn in the ex- stuck to the internal Cr2O3 layer. But, the entire surface oxide layer
ternal layer was ascribed to the rapid diffusion of Mn cations compared adhering to the substrate appeared to be weak. In Co/ZrO2-coated
to other cations (such as Fe and Cr cations) reaching from the Crofer sample, as shown in Fig. 7e and f, the surface oxide layer consisted of a
22APU to the Cr2O3 scale; therefore, the creation of Cr-Mn spinel was twofold oxide layer with the composition similar to the oxide scale
caused by the rapid diffusion of Mn in the direction of the steel and created on the surface of Co-coated sample. XRD analysis (Fig. 8b, c)

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Fig. 10. SEM cross-section image of: (a) Co-coated and (b) Co/ZrO2-coated samples after 100 h of cyclic oxidation in laboratory air at 800 °C.

also verified that the compositions of the surface oxide scales created on is anticipated to be proportionate with electrical conductivity, sup-
the Co-coated and Co/ZrO2-coated samples were similar. Fig. 9e shows posing a consistent conductivity of the oxide; it has been shown that the
that the external Co spinel layer was excellently stuck to the internal ASR of FSSs electroplated with Co is an approximately linear function of
Cr2O3 layer. Furthermore, the entire surface oxide layer adhering to the the Cr2O3 layer thickness [32]. A thin Cr2O3 layer is also advantageous
substrate appeared to be intense. since the danger of spallation increases by increasing oxide layer
The Cr2O3 layer with approximately 2.0 μm thickness was created thickness. The spallation of the protective Cr2O3 layer may result in
on the uncoated sample after 500 h oxidation (Fig. 9a), but the internal both increased Cr evaporation and creation of non-protective iron
Cr2O3 layer developed on the Co-coated sample (Fig. 9c) was only oxides. A higher boundary for suitable Cr2O3 layer thickness is about
around 1.5 μm, exhibiting that the creation of the external Co3O4 and 10 μm in many cases because the danger of oxide spallation and the
MnCo2O4 spinel layer decreased the development rate of the internal electrical resistance becomes large above that thickness in a manner
Cr2O3 scale. It is apparently indicated that the external spinel layer has that is not acceptable [33].
not only limited the outward diffusion of Cr but also repressed the in- EDX maps analysis was also performed on the surface of Co-coated
ward diffusion of O, finally resulting in the lower development rate of (Fig. 11) and Co/ZrO2-coated (Fig. 12) samples after 500 h of cyclic
the internal Cr2O3 scale on Co-coated Crofer 22APU [22,30]. The Cr2O3 oxidation in laboratory air at 800 °C. These figures undoubtedly are
layer on the Co/ZrO2-coated sample (Fig. 9e) had thickness of about useful for better describing areas of enrichment or depletion in certain
800 nm. This was remarkably thinner than the one on the uncoated and elements. The elemental mapping images in Figs. 11 and 12 indicate
Co-coated steels, showing that the incorporation of ZrO2 particles into that there is a small portion of inter-diffusion of ionic species, e.g. Mn,
Co coating decreased the development rate of a Cr2O3 layer on Crofer Cr, O, Co and Fe across the interface of coatings and substrate. It is
22APU, whereas it was placed in SOFC cathode-related situations. apparently indicated that a distinct layer with significant Co and to the
For the coated samples, two consecutive oxidation regimes appear less extent O, Mn, Cr, and Fe was formed on the Crofer 22APU surface
(Fig. 6a, b): a rapid oxidation on the first 100 h attributed to the oxi- (Figs. 11,12). In the Co/ZrO2-coated sample, the presence of ZrO2
dation of Co, and a much slower kinetic regime associated with the particles can be seen in this layer too (Fig. 12b). Formation of a thin
oxidation of the substrate. This prove by the cross-section analysis on layer of Cr and O in the coatings/substrate interface is also in good
oxidized samples for about 100 h. As shown in Fig. 10a, the Cr2O3 layer agreement with the EDS maps (Figs. 11b, c, and 12 c, d).
with 1.1 μm average thickness was created on the Co-coated sample The effect of ZrO2 particles on the development rate of Cr2O3 layer
after 100 h oxidation, but the internal Cr2O3 layer developed on the Co/ is explained by the reactive element effect, representing several orders
ZrO2-coated sample (Fig. 10b) was only around 0.5 μm. The average of decrease in the oxidation rate of similar kinds of FFS when used as
thickness of the external Co3O4 and MnCo2O4 spinel layers that were the interconnect [18–20,34]. It is clear that the addition of ZrO2 to the
created on the surfaces was about 7 μm after 100 h cyclic oxidation Co coating could inhibit effectively the growth of Cr2O3 scale. Near the
time. The thickness of external layers developed about 2 μm after 100 h ZrO2 particles, Cr2O3 tends to grow inward along the particles of ZrO2
in air at 800 °C. Compared to oxidized coated sample for 500 h at (Fig. 9e). It should be pointed out that only a small number of pores are
800 °C, the internal Cr2O3 layer thickness was thinner but the external observed beneath the oxide scales for the Co/ZrO2-coated steels, much
spinel layer have the same thickness. These results show that after fewer than those for the Co alloy coated samples. In research conducted
100 h oxidation, the Co coating is completely oxidized and converted to clarify the effect of the reactive element on the growth of the voids at
into a Co spinel oxide coating, and then, after 500 h of oxidation, the the oxide scale/alloy interface, adding minor Hf significantly improved
thickness of this outer layer of spinel oxide on both coated samples does the cyclic oxidation resistance of the NiAl alloy by suppressing the
not change. But the internal layer of Cr2O3 continues to grow for up to growth of voids at the oxide scale/alloy interface in both dry and humid
500 h, then after 100 h, its growth rate, especially for Co/ZrO2-coated atmospheres [27]. Among the different mechanisms suggested to il-
sample, reduces significantly. lustrate the effect of reactive elements (improvement of oxide nuclea-
A slow growth rate of the Cr2O3 layer is beneficial due to the fact tion [35,36], “sulfur” theory [37,38], “dynamic segregation theory”
that Cr2O3 has a low electrical conductivity and causes electrical [39]), the conversion of the oxide scale development mechanism is
missing of the SOFC systems. The electric conductivity of Cr2O3 is 0.022 accepted to present the most advantageous effects. Experiments by
S cm−1 at 800 °C [16], which is considerably lesser than the one of Co utilizing two-stage oxidation tests under 16O2–18O2 [40,41] clearly il-
oxides (6.7 6.7 and 60 S cm−1) [29]. Therefore, the thickness of the lustrated that outward diffusion of Cr ions is the prevalent mechanism
Cr2O3 layer is anticipated to be the most important ingredient for the for Cr2O3 development on Cr2O3-forming alloys.
electrical resistance of the sample [31]. The thickness of the Cr2O3 layer The addition of reactive elements in the Cr2O3 scale modifies the

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Fig. 11. EDX maps analysis on the cross section surface of Co-coated sample: (a) Co, (b) Cr, (c) O, (d) Mn, and (e) Fe after 500 h of cyclic oxidation in laboratory air at
800 °C.

ionic species diffusion, and inward O ion diffusion becomes the pre- interconnect utilization is the ASR of the surface oxide layers. High and
valent transport mechanism. Such conversion in the transport me- steady electrical conductivity is fundamental for metallic interconnects
chanism is attributed to the segregation of reactive element ions or under the work conditions of the SOFC. ASR is utilized to estimate the
second phase particles at the Cr2O3 grain boundaries. It results in ob- electrical conductivity of interconnects [42]. ASR evaluations were
structing the outward cation diffusion, diminishing the oxidation rate done for the uncoated, Co-coated and Co/ZrO2-coated samples after
and improving the oxide scale adherence. Such a change in the Cr2O3 cyclic oxidation experiment in laboratory air at 800 °C for 500 h as a
scale growth mechanism results in inhibiting the formation and coa- function of temperature. The ASR value of the studied samples mea-
lescence of cation vacancies at the metal/oxide interface. Void forma- sured within 650–800 °C increased with temperature (Fig. 13a). Cor-
tion at the metal/oxide interface is a result of the outward transport of relation between log (ASR/T) and 1/T was linear (Fig. 13b), which was
metallic ions through vacancies which allow their coalescence at the consistent with the semiconductor behavior, depicted with Arrhenius
interface to weaken the adhesion to the substrate [18]. equation [43]:

ASR = A.T. exp (−Ea/KT) (2)

3.4. Electrical behavior
where A is the proportional factor, T is the absolute temperature, k is
the Boltzmann constant and Ea indicates the activation energy for
Another essential characteristic for estimating the SOFC

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F. Saeidpour, et al. Corrosion Science 153 (2019) 200–212

Fig. 12. EDX maps analysis on the cross section surface of Co/ZrO2-coated sample: (a) Co, (b) Zr, (c) Cr (d) O, (e) Mn and (f) Fe after 500 h of oxidation in laboratory
air at 800 °C.

conduction. an extra heat treatment to make the coating dense [46,47]. In those
Fig. 13 shows that the ASR measured for all the samples is generally studies μm thick Cr2O3 layers were formed due to the heat treatment
less than the maximum allowed level for use in SOFC interconnects, i.e. necessary to increase the density of the powder. As the ASR measure-
100 mΩ cm2 [44]. The ASR values obtained for Co-coated Co/ZrO2- ments in Fig. 13 show, this would have a tremendous effect on electrical
coated steels was far lower than the uncoated one. As an example, the resistance at 800 °C. Therefore, metallic conversion coatings, as well as
ASR at 800 °C for Co-coated and Co/ZrO2-coated steels was 18.1 and coatings deposited with other techniques that do not require a high
14.5 mΩ cm2, respectively, while for the uncoated one, it was temperature heat treatment, seem to be the most suitable coating
35.6 mΩ cm2. This obviously exhibited the desired effect of deposited techniques for SOFC.
coating on obstructing the creation and development of high electrical The activation energy for conductivity (Ea) was estimated from the
resistance oxides, and creation of Co and Co-Mn spinels, which had less gradient of the log (ASR/T) versus 1/T graph (Fig. 13b) for all the three
electrical resistance and compatible thermal expansion with Crofer studied steels. The Ea values were calculated to be 25.14 kJ mol−1 for
22APU [19,24]. When ASR values were measured at 650 °C (Fig. 13a), the uncoated sample, 14.51 kJ mol−1 for Co and 8.571 kJ mol−1 for the
an important increase in ASR could be observed because of the far Co/ZrO2 coated steel. Co is a p-type dopant that has an important effect
thicker Cr2O3 layer on the steels [45]. on increasing the conductivity of spinel compounds such as MnCo2O4
In this paper coated samples exposed to 800 °C showed very low (60 scm−1), CoCr2O4 (7.4 scm−1) and CoFe2O4 (0.93 scm−1) [48]
ASR values. The reason for this is the very thin Cr-rich oxide layer. In compared to Cr2O3 (0.02 S cm−1) and (Mn,Cr)3O4 (0.5 S cm−1 for
several studies coatings have been applied as powder, with the need for MnCr2O4 and 0.02 S cm−1 for Mn1.2Cr1.8O4) [49]. The ASR values of

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F. Saeidpour, et al. Corrosion Science 153 (2019) 200–212

• The potential of Co and Co/ZrO 2 to function as protective coatings

on Crofer 22APU stainless steel was evaluated via cyclic oxidation
tests.
• The Co/ ZrO2 coating decreased the Cr2O3 layers' thickness from
about 2.0 μm on uncoated steel and around 1.5 μm on Co-coated
sample to ˜800 nm after 500 h oxidation in laboratory air at 800 °C.
• The Co/ZrO2 coatings could decrease the oxidation rates of the steel
during exposure to laboratory air at 800˚C after 100–500 h of oxi-
dation, as compared to the uncoated and Co-coated samples.
• ASR of the uncoated and coated Crofer 22APU steels was measured
in the temperature range of 650–800 °C, which revealed a semi-
conductor behavior.
• ASR evaluations at 800 °C in laboratory air exhibited that the lowest
ASR values were acquired for the Co/ZrO2-coated steels and was
equal to 14.5 mΩ cm2 at 800 °C after 500 h cyclic oxidation in la-
boratory air.

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